KR101315002B1 - Method for manufacturing abzo transparent conductive oxide - Google Patents

Abstract

PURPOSE: A method for manufacturing an ABZO transparent conductive layer is provided to improve electrical conductivity by a boron vapor diffusion process. CONSTITUTION: Boron is thermally diffused on a soda lime glass substrate (100). The boron is diffused on the soda lime glass substrate with vapor. An AZO layer (200) is formed by diffusion process. The AZO layer is annealed. A boron silicated glass layer (150) is formed on the soda lime glass substrate. [Reference numerals] (100) Soda lime glass substrate; (150) Form a BGS layer; (AA) Deposit an AZO layer (200); (BB) Annealing: boron diffusion

Description

Production method of AHO transparent conductive film {METHOD FOR MANUFACTURING ABZO TRANSPARENT CONDUCTIVE OXIDE}

The present invention relates to a method for producing an ABZO transparent conductive film.

Transparent conductive films are used in many electronic devices such as LCDs, OLEDs, solar cells, LEDs, and various touch panels. Until now, the main material of transparent conductive film is indium tin oxide (ITO), which has the most satisfactory performance in transparency and conductivity. However, In is a rare earth metal, which is rare and valuable because of its low reserves. Therefore, research is actively being conducted to find a substitute material for ITO for an increasingly conductive transparent conductive film. A promising alternative to ITO is AZO. AZO with Al added to ZnO does not have the same burden as ITO because it does not use rare earth, but the problem is that the conductivity is lower than that of ITO. In order to solve this problem, an attempt has been made to form a transparent conductive film by doping In oxide or boron (B) in addition to AZO. Accordingly, a method of forming a transparent conductive film by sputtering the target by doping boron to a ZnO or SnO ₂ target has also been attempted.

Zinc oxide exhibits n-type semiconductor characteristics due to internal lattice defects without additional doping, but these defects are not easy to control the concentration and are sensitive to changes in the external environment (humidity, temperature, etc.). Low reliability on Therefore, research has been actively conducted to develop ZnO-based transparent conductive materials which can control conductivity by forcibly injecting impurities from the outside and have excellent environmental resistance.

ZnO has the characteristics of ion crystals because of the large difference in electronegativity. Zn (II) has the properties of divalent cations, and O has the properties of divalent anions, so the ionic bonding properties are very strong. Popular n-type dopants and their sizes are shown in Table 1 (atomic radius and ion radius of Zn and n-type dopants).

Atomic radius (nm) Ion radius (nm) Quadruple B 0.087 0.025 C 0.067 0.029 Zn 0.142 0.074 Al 0.118 0.053 Ga 0.136 0.061 In 0.156 0.076 O 0.048 0.124

If much eco-friendly ions, such as Zn is trivalent n-type dopant in place of ^{2+ B 3+, Al 3+, Ga} 3+, In 3+ have an electrical conductivity is improved by the density of the electric vehicle increases e. The requirement for substituting a sufficient amount of dopant is that the size difference between Zn ²⁺ and other substitution ions must be within 15%, otherwise the crystal structure will collapse, making it impossible to substitute a sufficient amount. Since the difference in size between zinc ions and boron ions is about 66%, only a small amount of chemicals can be substituted, thus improving the electrical conductivity. Boron-substituted BZO is usually about 1x10 ^-3 Ω-cm even at the best resistivity, and the carrier density is usually less than 10 ²⁰ / cm ³ , which is a large difference in the amount of B that can be substituted. Because it is limited.

In the case of Al ³⁺ which is most commonly used as a dopant, the size difference according to the ion radius is about 28%, which is greatly improved compared to boron, but since the difference in size is more than 15%, the amount of Al that can be substituted is also limited. It is 2-5x10 ^-4 Ω-cm level and the transmitter density is 1-5x10 ²⁰ / cm ³ level, which is 5 ~ 10 times better than that of boron, but it is somewhat insufficient compared to ITO. In terms of size, the most preferable dopants are In ³⁺ and Ga ³⁺ , and the difference in size is 2.7% and 17%, respectively, and In can be injected in a large amount. The disadvantage is the high cost of the raw materials. Therefore, if the ion can be additionally implanted through thermal diffusion using the concentration gradient of boron on the surface of the Al-substituted AZO, it is expected that further electrical conductivity can be improved at low cost.

With this principle, the manufacturing of ABZO-doped transparent conductive film doped with B in AZO is more marketable as the manufacturing process is simpler, the cost is lower, and the electrical conductivity is higher.

Accordingly, an object of the present invention is to provide a new method for manufacturing a transparent ABZO transparent conductive film that can be easily and low-cost manufacturing a transparent conductive film made of ABZO to replace ITO.

Accordingly, the present invention provides a method for manufacturing a transparent conductive film substrate made of ABZO by thermally diffusing or vapor diffusing boron on a soda lime glass substrate, forming an AZO layer, and annealing the boron to diffuse the boron in the AZO layer. .

In addition, the present invention is to form a BSG (Boron Silicated Glass) layer on a soda lime glass substrate, to form an AZO layer thereon, to anneal it to diffuse the boron in the AZO layer to produce a transparent conductive film substrate of ABZO To provide.

In addition, the present invention provides a method for producing a transparent conductive film substrate in which the annealing temperature is 200 to 700 ° C in the method for producing a transparent conductive film substrate.

In addition, the present invention provides a method for producing a transparent conductive film substrate made of ABZO by simultaneously doping Al and B while forming a ZnO layer on a substrate using chemical vapor deposition.

According to the present invention, the boron is diffused on an inexpensive soda-lime glass substrate to form an AZO layer, and the annealing is performed to diffuse boron into the AZO layer, thereby forming an ABZO transparent conductive film, thereby greatly improving electrical conductivity compared to AZO, while improving transparency. In addition, the transparent conductive film substrate maintained at a high level can be manufactured in a simple and low cost process.

1 is a schematic diagram showing a method for manufacturing an ABZO transparent conductive film using boron vapor phase diffusion according to an embodiment of the present invention.
2 is a schematic diagram showing a method of manufacturing an ABZO transparent conductive film using a BSG layer and an AZO layer according to another preferred embodiment of the present invention. The content of B in the BSG layer was found to be 10 to 18% to improve the electrical conductivity.
3 is a schematic diagram showing a method of manufacturing an ABZO transparent conductive film using CVD according to another preferred embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1 illustrates a method of forming an ABZO transparent conductive film on a soda lime glass substrate 100. Soda lime glass substrate 100 is a low-cost glass substrate widely used for display. Boron is first diffused into the soda lime glass substrate 100. The boron diffusion implantation may be performed by placing a soda-lime glass substrate 100 in a chamber and forming a vapor diffusion or boron atmosphere that is treated with a boron atmosphere and heat treatment simultaneously with heat treatment. After the chamber is low vacuumed, the boron partial pressure may be adjusted to appropriately control the pressure of the atmosphere, and the heat diffusion temperature may be performed at about 200 to 600 ° C. Through such a boron diffusion step, boron penetrates into the surface of the soda lime glass substrate 100.

Next, an AZO layer is formed on the soda lime glass substrate 100 into which boron is injected. The formation of the AZO layer is made by doping Al to the ZnO layer, preferably using a CVD process. Other methods such as sputtering may also be used, but CVD is advantageous when considering mass productivity.

Next, the soda lime glass substrate 100 on which the AZO layer 200 is formed is annealed at 200 to 700 ° C., preferably 400 to 600 ° C. in the chamber. In the annealing process, the boron diffused on the surface of the soda lime glass substrate 100 is diffused into the AZO layer, thereby ultimately forming the ABZO 210 transparent conductive film. This process is very simple and can be carried out at low cost, which is very advantageous for mass production.

FIG. 2 illustrates another example of depositing a BSG (Boro-Silicated Glass) layer 150 on a soda-lime glass substrate 100 using a PECVD process. At this time, it is possible to adjust the content of Boron in the BSG within 20%. Preferably, when the amount of B is adjusted to 2 to 10%, the amount of diffusion of B is appropriate, which is most advantageous for improving the electrical conductivity. Once the AZO layer 200 is formed on the substrate on which the BSG is deposited, annealing is performed to diffuse boron in the BSG 150 layer into the AZO layer 200 to change the AZO layer to the ABZO 210 layer. The BSG 150 layer may be formed by any conventional method, but preferably, PECVD may be used. The annealing temperature for boron diffusion is 200 to 700 ° C, preferably 400 to 600 ° C.

Meanwhile, as illustrated in FIG. 3, the ABZO layer 210 may be formed by simultaneously doping ZnO with Al and B on the soda lime glass substrate 100 by CVD.

The boron-doped ABZO layer 210 is less susceptible to damage to the film due to stress, so that a sufficient amount of Al can be injected, thereby improving electrical conductivity while maintaining excellent light transmission due to boron.

In the above embodiments, the thickness of the ABZO 210 layer may be about 0.1 μm to 2 μm, and the sheet resistance is 5 to 10 Ω / □, which may replace the ITO in a specific application (solar cell, touch pad, etc.). Indicated.

It is to be understood that the invention is not limited to the disclosed embodiment, but is capable of many modifications and variations within the scope of the appended claims. It is self-evident.

100: soda lime glass substrate
150: BSG
200: AZO layer
210: ABZO

Claims (6)

A method of manufacturing a transparent conductive film substrate made of ABZO by thermally diffusing or vapor diffusing boron on a soda lime glass substrate, forming an AZO layer, and annealing the boron to diffuse the boron in the AZO layer. A method of manufacturing a transparent conductive film substrate made of ABZO by forming a BSG (Boron Silicated Glass) layer on a soda lime glass substrate, forming an AZO layer thereon, and annealing the boron to diffuse the boron in the AZO layer. The method for producing a transparent conductive film substrate according to claim 1 or 2, wherein the annealing temperature is 200 to 700 ° C. A method of fabricating a transparent conductive film substrate using a chemical vapor deposition method to form a ZnO layer on a soda lime glass substrate and simultaneously doping Al and B to form an ABZO layer. The method of claim 2, wherein the concentration of boron contained in the BSG layer deposited on the soda lime substrate is 1 to 20%. The method of claim 5, wherein the concentration of boron contained in the BSG layer deposited on the soda lime substrate is 2 to 10%.

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